Manufacture of motor fuels



v*April vl0, 1945. LE oY G. s ToRY i 2,373,612 MANUFAGTURE OF MOTOR`FUELS Filed March '21, l19:69

` or without a hydrogen and HC1. or Bh. HF andNi; and liquid hydrogen Patented Apr. 10,

UNITEUSTATES PATENT-*orner -l asili-.lillyA y l l vLe Boy G. story, white Plains, N. Y..

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assignments, to'The Texas assigner. br Com New York, N'. Y., a corporation of Delaware Application March' 2l, 1939, Serial No. 283,114

c (on zoet-cual "nurv invention relates to the manufacture o: motor fuels and has todo more particularly with from oleilns and isoparaillns.

- c In accordance with 'the-invention. oleane, in-

cluding normalv and iso-olefinsand are subjected tothe action ofa catalyst in the presence chiefly saturated, branch chain hydrocarbons within thegasoline boiling range are formed.

of hydrogen whereby high antiknock..

A the production of high'antiknock hydrocarbons cracking still gases.are suitable. although gasoline' hydrocarbons or heavier,

speclnc applications -o'f the invention will now V =be'discussed.

object of the present invention is to ohtain alkylatlon of ,with olefins, and

' desirable side reactions and the yield of desired Pmvent .increase is to prevent catalyst deterioration whereby the life of the catalyst is substantially increased.

It 'has been known heretofore that may be alkylated with oleris in the presence of catalysts, such as sulfuric vacid. or aluminum ch1o rlde, providing nhigh ratio ofisoparamns to ole tins is maintained in the reaction mixture.. In

' these operations,l however, side reactions and deterioration of 'the catalyst occurs. Particularly if a high ratio of iso to oleilns is not main- Y. has n ow been found that it is advantageous to carry out reactions involving alwlation in the- "Y presence of hydrogen or a hydrogen producing amountof hydrogen may vary considerably, for example a hydrogen pressure of 50, 100, 150, 300,

500.1000 or3000poundsma'ybeused, 'Itisprefr erable to use a hydrogen pressurel of about 50 t0 500 or 1000 pounds. The hydrogen vmay function tocontrol the course of the reactions `'rire catalysts are sulfuric acid o: about so to 100% und preferablyelcout 94 to 98% HnSOqa metallic halide alone. or preferably 'with a hydrogen halide'. such as AlCh or BF; and HC1 or HF; a'metallic halide and` a metal, with halide, such asAlCh, Al,

iiuoride.

bollin P01" MUS 'hy' Y the yield ci'. gasoline hydrocarbons-mbstantially material or ahydrogen' containing gas. The 30.

In che' alkylauonof low boiling iconernmnr. with olefins, for example the alkylation of isobutane with C: or C4 oleilns, in tbe presence of sulfuricracld, although low temperatures of -10 to about 30 C. and la'lal'ge excess of xisobutane isused',

considerable catalyst. deterioration is experienced However, by eiecting vizheJ-eacticn under several atmospheres of hydrogen such catalyst deteriora-' tion is substantially v,reduced The. alkylation of iso temperatures is difilcult because of rapid .catalyst deteriorationand tendency 4toward polymerization.' particularly of the isooleflns. By using .several atmospheres of hydrogen pressure, the catalyst deterioration Aand tendency to 'polymerize may belargely prevented and increased., A

'Ihe'alkylation of .isoparamns with lower boiling oleiins, such as. ethylene and propylene is considerably facilitated 'by operating in the presence of hydrogen.- Higher temperatures may be used, more selective reaction or less catalyst deterioration may be obtained.

VTheaccompanying drawing is a diagrammatic sketch of one form of apparatus for carrying out the process of the invention.

Referring to the drawing, vtile hydrocarbons l vmay be introduced into the system through branch line l, which communicateswith the main line 2 leading to a reaction chamber 3. Hydrogen may be introduced. through the branch line= l which also communicates with theline -2. While one line is shown for introducing the hydrocar- 'The temperatures of operation will depend and oleilnsmixed with normal parlili separate line for boris, it isto be understood that any number of 'linesmaybeusedincaseitisdesirabletosepl olensandiscparamns. 'Alsoa' arately inject the injecting the hydrogen may be used, if desired. In the reactor 3 the hydrocarbons and hydrogen are intimately contacted with the catalyst introduced through the line 1.. The reactor may be provided with a suitable v agitator or other means of contact, whereby'the catalyst, hydrogen andhydroca asuitable provided;

l'rue products are conducted from the reactor a throughithe line l to a separator Il. Any portion of the products bons -of 2 to' 5 carbon atoms, for example veither straight run or cracked 'are contemplated Some ofthe more less side reactions and are intimately conwithdrawn through line l Il by the pump I2. 'I'he lines B. Il and pump l2 constitute aninternal recycle 'stream into which the hydrocarbons and hydrogen from lines I, v5 and 2 are preferably injected. It is desirable to maintain a relatively high ratio of products rei cycled internally to the fresh charge introduced through the line 2.

In the separator l hydrocarbons separate from the acid which collects in the lower portion of the separator. The spent acid is withdrawn through the line i4 and may be forced by the pump l5 through the line 'i to the reactor 3. Any portion of the spent acid may be withdrawn from the system through the line I8. Fresh make-up acid maybe charged to the system through the line' I3 which communicates with the line 1.

'I'he hydrocarbons collecting in the upper portion of the separator l0 are withdrawn through the line 20. Any portion or all of the hydrocarbons may be returned tothe reactor 3 through the branch line 2|. The remainder of the hydrocarbons is conducted through the branch line 22 to a fractionator 24, which is preferably maintained under sulcient pressure to maintain the hydrocarbons in the liquid phase. Provision is made whereby hydrogen may be withdrawn from' the top of the fractionator through the line 25 and discharged `from the system through the branch line 26 or recycled to the system through the branch line 28 which communicates with the line 2i leading to' the reactor 3.

The hydrocarbons are withdrawn from the fractionator ,2d through the line 33 and are preferably passed through the line 3| to a stabilizer 32. In the stabilizer the light hydrocarbons, comprising mainly isobutane, are separated and released from the top ofthe stabilizer through the line 3d. Any portion or'all ofthe gases may be` recycled through the branch line 35, pump 36 and line 38 -to the internal recycle stream in line il. The stabilized 'alkylate is withdrawn from the stabilizer through the line 60.

Obviously many modifications and variations of the invention, as herelnbefore set forth, may be made without departing from the spirit and seme thereof, and therefore only such limitations should' be imposed as are indicated in the ap-l pended claims.

I claim: 4

l. In a process for the catalytic alkylation of a low-boiling isoparaiiln with a, low-boiling olefin to produce gasoline'hydrocarbons of high antiknock value, .wherein the low-boiling isoparamn uand olen are reacted in liquid phase under alkylation conditions in an allqlatio'n reaction zone in the presence of an eiective alkylation may be recycled to the-reactor through the linev catalyst within the temperature range of about -10 to 100 C. and with the isoparailin maintained in molar excess of the olen in said zone, and wherein some `catalyst deterioration normally tends -to take place, the improvement which comprises maintaining throughout said reaction zone during the period of said alkylation reaction a substantial amount of extraneously added' hydrogen to provide a hydrogen pressure within said zone of -3000 pounds per Vsquare inch, whereby s aid catalyst deterioration is minimized.

2. A process according to claim 1 in which the atalyst is strong sulfuric acid, and the temperature is maintained at about. -10 to 30 C., and the hydrogen pressure is about 50 to 500 pounds per square inch.

3. In a process for the catalytic alkylation of a low-boiling isoparaiiin with ethylene in the presence of an aluminum halide and a hydrogen halide and a maintained molar excess of isoparain to ethylene, the improvement which comprises carrying out the alkylation reaction in a reaction zone at a temperature of about 0 to '15 C.,'and

maintaining a substantial amount of extraneously added hydrogen throughout the said reaction zone during the said all-tylationl reaction to provide a hydrogen pressure within said zone of about 150-1000 pounds per square inch and maintain the hydrocarbons essentially liquid phase, whereby catalyst deterioration is minimized.

4. A process according to claim 1 wherein the alkylation catalyst comprises aluminum chloride.

-5. A process according tor claim 1 wherein the alkylation catalyst comprises hydrogen fluoride;

6. In a continuous process for the catalytic alkylation of an isoparain with an'olen to produce gasoline hydrocarbons of high anti-knock value, wherein feed hydrocarbons comprising the the said lreaction zone where hydrocarbons are in contact with the catalyst and the entire alkylation reaction takes place in the presence of the extranoously-added hydrogen and under a hydrogen pressure of about 5043000 pounds per square LE ROY G. STORY. 

